Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS6083490 A
Publication typeGrant
Application numberUS 09/068,290
PCT numberPCT/AU1996/000697
Publication dateJul 4, 2000
Filing dateNov 6, 1996
Priority dateNov 6, 1995
Fee statusPaid
Also published asEP0880561A1, EP0880561A4, EP0880561B1, WO1997017406A1
Publication number068290, 09068290, PCT/1996/697, PCT/AU/1996/000697, PCT/AU/1996/00697, PCT/AU/96/000697, PCT/AU/96/00697, PCT/AU1996/000697, PCT/AU1996/00697, PCT/AU1996000697, PCT/AU199600697, PCT/AU96/000697, PCT/AU96/00697, PCT/AU96000697, PCT/AU9600697, US 6083490 A, US 6083490A, US-A-6083490, US6083490 A, US6083490A
InventorsDavid Graham Ellis, Michael Ary Bos
Original AssigneeM&J Consultants Pty Ltd, David Graham Ellis
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
UV absorbing compositions
US 6083490 A
Abstract
A process for producing a liquid dispersion of an inorganic oxide selected from zinc oxide, titanium dioxide and iron oxide, and having a particle size in the range of 0.02 to 30 μm, the process including comminuting the oxide in the presence of the liquid, the liquid being constituted by or including a component having available hydrogen and/or oxygen ions. The liquid is selected from one of an alcohol, ester, hydrogenated ester or polymer containing hydroxyl or hydrogen group(s). The stable dispersion which does not aggregate or agglomerate is suitable for use in topical preparations such as skin care or therapeutic products, cosmetics or hair care products.
Images(1)
Previous page
Next page
Claims(17)
What is claimed is:
1. A process for producing a dispersion of particles of an inorganic oxide selected from zinc oxide, titanium dioxide or iron oxide in liquid, the process including comminutng the oxide in the presence of the liquid to produce smaller particles with fresh cleavage surfaces to provide a particle size in the range of from 0.025 to 0.5 μm, wherein the liquid is selected from the group consisting of alcohols, esters, hydrogenated esters and polymers containing available hydroxyl group(s) and wherein the liquid is free of dispersing agent.
2. A process according to claim 1 wherein the liquid selected from the groups consisting of dioctyl phthalate, glycerol mono-oleate, glycerol mono-stearate, isopropy myristate, diethyl phthalate, propylene glycol dicaprylate/caprate, glycerol tricapylate/caprate, methyl laurate, propylene glycol, methyl oleate, dioctyl adipate and mixtures thereof.
3. A process according to claim 1 wherein the inorganic oxide is comminuted to provide a particle size in the range of from 0.04 to 0.1 μm.
4. A process according to claim 1 wherein the particles are comminuted in the liquid from a particle size of 0.2 μm to 10.0 μm to provide a particle size in the range of 0.04 to 0.1 μm.
5. A process according to claim 1 wherein the liquid is substantially free of water.
6. A process according to claim 1 wherein the comminuting is carried out using a ball mill, bead mill, attritor mill or sigma mixer.
7. A process according to claim 1 wherein the inorganic oxide is zinc oxide.
8. A process according to claim 1 wherein the comminuting is carried out at a temperature in the range of about 50 to 150° C.
9. A process according to claim 1 wherein the inorganic oxide is added in an amount in the range of 10% to 95% by weight of the final dispersion.
10. A process according to claim 1 wherein the surface area of the particulate inorganic oxide is from about 6m2 per gram of inorganic oxide to about 50m2 per gram.
11. A process according to claim 1 wherein the disperison in incorporated into a topical preparation for use in skin care, therapeutic treatment, a cosmetic or in hair care.
12. A process according to claim 1 wherein a colouring agent is added to the dispersion to provide a cosmetic formulation.
13. A process according to claim 1 wherein the dispersion is incorporated into a cosmetic selected from the group consisting of lipstick, face powder mascara, eye shadow and blush.
14. A process according to claim 1 wherein the inorganic oxide is zinc oxide present in an amount of from 20 to 30% by weight of the composition and the dispersion is used in manufacture of a sunscreen.
15. A process according to claim 1 wherein the dispersion is incorporated into a composition selected from the group consisting of a coating and plastics composition.
16. The process according to claim 15 wherein the composition is semi transparent.
17. The process according to claim 15 wherein the composition is clear.
Description
FIELD OF THE INVENTION

The present invention relates to UV absorbing compositions, in particular to UV absorbing composition including a surface modified inorganic oxide dispersed in particulate form.

BACKGROUND OF THE INVENTION

The invention will be now specifically described in reference to the use of modified zinc oxide as the UV attenuating oxide, however the invention also extends to other inorganic oxides including titanium dioxide and Iron oxide.

Zinc oxide scatters some wavelengths of light and absorbs other selected wavelengths of light. It exhibits very strong absorption at wavelengths just short of the visible spectrum. It Is a strong UVB absorber at the 210-320 nm wavelength and also at the UVA 320-840 nm wavelength. At wavelengths longer than 370 nm. protection is provided by scattering and at wavelengths shorter than 370 nm, protection is achieved predominantly by absorption. Zinc oxide exhibits a strong semi-conductor absorption in the ultraviolet region. The optimum size of a zinc oxide particle for attenuation of the ultraviolet radiation is less than 0.06 μm for the wavelength range 300-400 nm. Absorption is the dominant mechanism for attenuation of ultraviolet radiation in the wavelength range of 300-400 nm.

Zinc oxide has been used as a white reflective pigment (particles size 1.0-20 μm) and as a UV absorber (particles 0.3-5 μm) for many years. The earliest form of presentation of zinc oxide as a sunscreen agent is a pigmented cream which is used to protect various parts of the exposed body, particularly the nose. Although this zinc oxide cream has its place, the conspicuous nature of the cream when on the skin reduces Its cosmetic appeal significantly. Attempts at turning a disadvantage to advantage has led to recent variations of the zinc oxide cream in which a coloured pigment is used to produce a brightly colour cream such as blue, red, yellow or green cream. Such modifications, although popular particularly with the young, have limited cosmetic appeal to the more general population.

It is highly desirable that the UV attenuating substance be invisible on the skin with any colour variation in the sunscreen formulation being adjusted to achieve a desired cosmetic effect.

To overcome this visual problem and also improve the performance as a sunscreen, zinc oxide with a particle size of 0.1-1.0 μm has been used in order to increase UV absorption and decrease reflectance of light. Moreover zinc oxide with a particle size less than 0.1 μm becomes invisible when rubbed onto the skin. However prior art attempts to use microfine zinc oxide has led to difficulties in formulation. The fine zinc oxide powder is difficult to keep in suspension. The particles irreversibly bond during manufacture, and when formulated into a dispersion, tend to aggregate, agglomerate and then settle out. Prior art sunscreen creams incorporating zinc oxide in this particle size range appear white on the skin, develop a settled out layer which is difficult to disperse. Moreover the prior art formulations tend to develop a clear top layer.

Prior art zinc oxide formulations are also limited in terms of the amount of zinc oxide that could be mixed into the formulation (up to about 10% by weight) which limits the blockout effect of the sunscreen. To disperse the zinc oxide in the formulation, various wetting agents, in combination with anti-settling agents have been used, this effectively decreasing the amount of UV active that can be included in the formulation, adding to the cost of manufacture and increasing the risk of an adverse skin reaction.

When zinc oxide is freshly made into a fine powder by burning fumed zinc metal vapour, oxygen will bond onto the fresh zinc oxide surfaces. This oxygen bonding then prevents any further bonding with hydrogen or oxygen ions when the zinc oxide comes in contact with an ester or alcohol and means that this zinc oxide is prone to agglomeration, aggregation, settling and hence whitening.

Furthermore, freshly made zinc oxide can absorb carbon dioxide which leads to the formation of carbonates on its surface. This absorption of carbon dioxide thus inhibits the UV absorbing properties of the zinc oxide.

SUMMARY OF THE INVENTION

We have surprisingly found that it is possible to produce a stable oxide containing product which is less prone to aggregation, agglomeration or settling out to hard layer and where there is some settling, redispersion of the oxide can be achieved easily.

We have found that one or more of the problems attending the prior art may be avoided, or at least partially mitigated by comminuting, eg Intensive milling, the oxide in the presence of a liquid being constituted by or including a component having available hydrogen ion and/or oxygen ion.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a particle size distribution plot towards zinc oxide as prepared by Example 6, showing vesicle size (nm) in the abscissa; and

FIG. 2 is a particle size distribution plot towards zinc oxide dispersion as prepared by Example 10, showing solid particle size (nm) in the abscissa.

Accordingly the present invention provides, in one aspect, a process for producing a dispersion of particles of an inorganic oxide selected from zinc oxide, titanium dioxide or iron oxide in a liquid, the process including comminuting the oxide in the presence of the liquid, the liquid being constituted by or including a component having available hydrogen and/or oxygen ions.

Without wishing to limit the invention in any way, it is believed that when zinc oxide crystals are comminuted during the process of the invention, they produce smaller particles with fresh cleavage surfaces, these surfaces when produced by comminution In the liquid, bond to available hydrogen ion and/or oxygen ion to form zinc oxide which is both encapsulated and bonded to a film of the liquid. This gives a very stable product which does not aggregate, agglomerate or settle out to a hard layer.

Preferably the oxide is comminuted to a particle size of less than about 30 μm. More preferably the oxide Is not comminuted below a particle size of about 0.025 μm, preferably about 0.04-10 μm. A comminuted particle size of about 0.04-0.1 μm is particularly preferred.

The component containing available hydrogen ion and/or oxygen ion may be a substance or compound having one or more hydroxyl groups or hydrogen groups. Preferably the liquid is selected from one of an alcohol, ester, hydrogenated ester or polymer containing hydroxyl group(s) or hydrogen group(s) or mixtures of two or more of the foregoing.

Examples of suitable liquids may be selected from the group consisting of dioctyl phthalate, glycerol mono-oleate, glycerol mono stearate, isopropyl myristitate, diethyl phthalate, propylene glycol dicaprylate/caprate, glycerol tricaprylate/caprate, methyl laurate, methyl oleate and dictl adipate.

Preferably the liquid in which comminution takes place is substantially free of water. More preferably the liquid is free of water.

Comminution of the oxide may be carried out by milling. Milling may be achieved by any suitable method. Milling may be carried out using a ball mill, or other intensive mill such as a bead mill, attritor mill or sigma mixer.

Preferably the process of the invention is carried out by adding the oxide in the particulate form to the liquid whilst milling occurs although the oxide may be combined with the liquid and the mixture milled. The initial particle size of the oxide may be in the range of about 0.1 μm to 10.0 μm.

Preferably the oxide is zinc oxide. The zinc oxide used in the present invention may be crystalline zinc oxide. Amorphous porous zinc oxide is preferred where a very small comminuted particle size is desired as it is easier to mill down.

Preferably comminution occurs at an elevated temperature. The elevated temperature may be in the range of about 50° to 15° C. The oxide may added in an amount in the range of about 5% to 95% of the final dispersion.

In a further aspect, the present invention provides a liquid dispersion of an inorganic oxide in particulate form, the oxide selected from zinc oxide, titanium dioxide and iron oxide, wherein the oxide has a particle size in the range of about 0.02-30 μm and wherein the liquid is constituted by or includes a component having an available hydrogen ion, wherein the surfaces of the oxide particles are bonded to the available hydrogen ions and/or oxygen ions.

The oxide dispersion of the invention may be produced by the process of the present invention.

Preferably the oxide is present in the dispersion in an amount of about 5% to 95% by weight. Preferably the oxide is present in an amount of at least about 10% by weight, more preferably greater than about 20% by weight of the dispersion. The surface area of the particulate oxide in the dispersion may be about 6m2 per gram of oxide to about 50m2 /g, more preferably about 20 to about 30m2 /g.

Preferably the liquid component of the dispersion is selected from an alcohol, ester, hydrogenated ester or a polymer containing available hydrogen ion, for example, hydroxyl groups or hydrogen groups or mixtures of one or more thereof.

Preferably the dispersion of the oxide includes oxide in a particle range of about 0.4 to 10 μm, more preferably about 0.04-0.5 μm.

A zinc oxide powder has a refractive index of 1.9-2 with an oil absorption factor of 32.3. In its natural form. It is one of the whitest pigments available, however when it is milled to a particle size less than 0.1 μm in the liquid containing available hydrogen ion, it exhibits a distinctive yellow colour. This is believed to be due to scattering of light, similar to the yellow colours in opals which also scatter light with 25 nm crystals.

Preferably the oxide is zinc oxide.

The dispersion of the present invention has a wide range of applications in which its UV absorbent properties may be utilised. In particular, the zinc oxide product of the present invention also has antioxidant properties which also makes it useful in many applications.

The oxide dispersion of the present invention may constitute or be included In topical preparations such as skin care or therapeutic products, cosmetics or hair care products. The dispersion of the invention may be used in coloured cosmetics such as lipsticks, face powders, mascara, eye shadows, blushers etc. The dispersion may also be included In stick products such as an anti-chap stick.

The present invention provides a sunscreen composition, the composition including a zinc oxide dispersion in accordance with the present invention.

By appropriate selection of the oxide loading in the suspension (for example, about 20% to 30% oxide), the dispersion of the invention may be incorporated into aerosol products. The product of the Invention may be incorporated into hair care products to provide UV protection.

The dispersion of the invention also has application in the area of coatings and films. The invention Is particularly suitable in instances where a clear finish is required such as in the case of clear lacquers, varnishes and shellacs. In this case, the zinc oxide acts both as a UV absorber and an antioxidant. In the case of a timber coating product, the zinc oxide acts as a UV absorber and by soaking into the timber grain protects the timber product itself.

The dispersion of the invention may be incorporated into latex coating emulsions.

The present invention also finds application in the area of printing inks and is particularly suitable for natural pigmented inks wherein the-oxide may act as an antioxidant and UV absorber.

The product of the invention may also be incorporated into plastic products to use its antioxidants and/or UV absorbing properties. It may be incorporated into addition polymers such as PVC, and polyolefins or condensation polymers such as polyurethanes. The dispersion of the invention may be incorporated in the injection, blow moulding, casting or extrusion stage.

The present Invention also has application in paints as a UV absorber and/or antioxidant. The Invention also finds particular application in the production automotive finishes such as clear film so as to provide more resistance to scratching and abrasion.

The present invention accordingly extends to the abovementioned compositions or formulations including an oxide dispersion in accordance with the invention.

In order that the invention may be more readily understand, we provide the following non limiting examples.

METHOD

Zinc oxide, titanium dioxide or ion oxide may all be milled in a liquid including a component having available hydrogen ions. Milling may be carried out an intensive mills such as a ball mill, bead mill, attritor mill, edge runner, Z arm or sigma mixer or the like.

Example 1

1220 g zinc oxide 813 g dried tridecanol

The tridecanol was loaded into a bead mill with 10 mm PSZ ball. Milling was started and the zinc oxide fed into the mill, continuously at a slow feed rate. The temperature was allowed to rise to 50° C. The zinc oxide was milled for about 12 hours to disperse all the zinc oxide and the particle size was checked against a stand. A dispersion of zinc oxide particles of the size less than 0.2 μm dispersed in tridecanol was produced.

Example 2

1220 g zinc oxide

813 g isopropanol

The isopropanol was loaded into a pre mix tank of a bead mill. Zinc oxide was added slowly and continuously. The pre-mix is fed into a bead mill and mixed for six hours and the particle zinc oxide checked against the standard and a dispersion of zinc oxide particles of the size less than about 0.15 μm dispersed in isopropanol was produced.

Example 3

1120 g zinc oxide

813 g glycerol tricaprylate

The glycerol tricaprylate and zinc oxide were loaded into a pre mix tank. The pro mix was mixed and fed into a triple roll mill. The zinc oxide/glycol tricaprylate dispersion was milled until the particle met the standard after three passes.

Example 4

Coated zinc oxide for use in a polyvinyl chloride compmosition was prepared by intensive bead milling of zinc oxide using small bead of 1 mm diameter. Milling was conducted in dioctyl phthalate until a zinc oxide particle size in the range of from 40 to 70 nm was provided. The coated zinc oxide was used in preparing the polyvinyl chloride composition detailed below.

______________________________________Polyvinyl Chloride Composition                 Kg______________________________________PVC Resin K-66        100Dioctyl Phthalate     50Lubricant Wax           0.5Calcium/Zinc Stabiliser                   2.085% Zinc Oxide encapsulated (coated)                   5.0milled in DOP______________________________________

The resin mix composition was run on a double roll mil @180° C. for 3 minutes to give a clear sheet

Example 5

Coated zinc oxide was prepared by ball Intensive milling of zinc oxide in the presence of a glycerol tricaprylatelcaprate mixed ester. Milling was conducted in an intensive bead mill using bead of 1 mm diameter at 80° C. until the particle size of about 40-70 nm was provided. The zinc oxide was used in preparing a water based printing varnish detailed below.

______________________________________Water Based Printing Varnish                Kg______________________________________Joncryl 74 (acrylic polymer resin)                55Emulsion             32Jonalec 26 (acrylic polymer resin)                585% Zinc Oxide Coated                3Butyl Cellosolve     5                 100.0______________________________________

Mix with high speed mixer

Example 6

Coated zinc oxide was prepared by the method described in Example 5 and used to prepare the oil based printing varnish detailed below.

______________________________________Oil Based Printing Varnish                  Kg______________________________________Pentalyn 833 (pentaerythritol ester)                  20Pentalyn 858 (pentaerythritol ester)                  20Micronised PE Wax      15Micronised PT Wax        0.5Long Oil Linseed Alkyd 15Megasol 52 Solvent (hydrocarbon solvent)                   26.585% Zinc Oxide Coated  3                   100.0______________________________________

Mix with high speed mixer

The zinc oxide particle size distribution (nm) in an example of a dispersion in accordance with the invention has a number-weighted gaussian analysis. (Vesicles) as follows:

______________________________________GAUSSIAN SUMMARY:______________________________________Mean Diameter = 184.8 nm            Chi Squared = 0.103Stnd. Deviation = 85.6 nm (46.3%)            Baseline Adj. = 0.000%Coeff. of Var'n = 0.463            Mean Diff. Coeff. = 2.32E-08 cm2/s______________________________________

Cumulative Results: 25% of distribution<113.15 nm 50% of distribution<154.51 nm 75% of distribution<211.56 nm 99% of distribution<457.08 nm

The distribution may be represented as shown in FIG. 1.

Example 7

Sunscreen Lotion

______________________________________Phase A 60° C. Mix until dispersed.                 Kg______________________________________Zinc Oxide            150"Elafac" (glycerol ester)                 50"Minno 21" (dispersing agent)                 50"Bridge 58" (emulsifier)                   3.0______________________________________

Phase A was prepared by milling in a bead mill using 1 mm beads over a period to provide coated zinc oxide particles of size 100 to 400 nm.

______________________________________Phase B Blend at 60° C.______________________________________"Keltanol" Solution (gum suspending agent)                   0.3"Carbopol" 974 (thickener)                   0.3______________________________________

Phased

"CA24" Preservative 0.2

Procedure

Add Phase B to Phase A. Mix until smooth. Then with Propeller mixer causing vortex add Phase D--mix until uniform.

Example 8

Sunscreen Lotion

______________________________________Phase A 40° C. Mix until disperses.                  Kg______________________________________Cupl Pic (glycerol ester)                   2.0Minno 21 dispersing    10.0Titanium dioxide (Micronisers) coated                  15.0Zinc Oxide (Micronisers) coated                  12.5______________________________________

Phase A was prepared by milling the titanium and zinc oxide composition with the ester in a ball mill using beads of size 1 mm diameter to provide a particle size of 100 to 400 nm.

______________________________________Phase B 40° C.Water            60.3Phase C Dry blendVeegum            0.70Keltanol         0.3Phase DCA24 Preservative            0.2______________________________________

The sunscreen composition was prepared by adding. Phase C to Phase B and mixed until the composition was smooth. With proper mixing (Propeller causing a vortex) Phase A was added and the composition missed until uniform. Phase D was then added and the resulting composition mixed until uniform.

The sunscreen lotion provides a high level of UV protection without significant whitening of the skin.

Zinc oxide can be used as a protector for light fastness of cheaper and expensive pigments in printing inks and overprint varnishes. Moreover it protects clear varnishes which degrade in the presence of ultraviolet light.

Example 9

Coating Composition The coated zinc oxide prepared in accordance with Example 5 may be incorporated Into an acrylic emulsion coating composition for use as a timber finish or other coating application.

The milling is conducted in the absence of water and the coated zinc oxide mixture is subsequently dispersed In water. The resulting composition may be used in forming an emulsion with acrylic resin or may be incorporated into a preformed acrylic resin emulsion.

Example 10

The zinc oxide single distribution is an example of a dispersion of the invention for use in coating or printing varnish compositions as shown below and is graphically represented in FIG. 2.

NUMBER-Weighted NICOMP DISTRIBUTION Analysis (Sold Particles)

______________________________________NICOMP SUMMARY:______________________________________Peak Number 1: Mean Diameter = 80.0 nm                   Number: 96.85%Peak Number 2: Mean Diameter = 325.1 nm                   Number: 3.15%______________________________________

Mean Diameter=90.4 nm Fit Error=2.737 Residual=12.165

______________________________________NICOMP SCALE PARAMETERS:______________________________________Min. Diam. = 30.0 nm Plot Size = 45Smoothing = 3        Plot Range = 100______________________________________

______________________________________Run Time = 0 Hr 11 Min 15 Sec               Temperature = 20 deg C.Count Rate = 466 Khz               Viscosity = 1.002 cpChannel #1 = 4027.8 K               Index of Ref. = 1.333Channel Width = 45.0 usec______________________________________

______________________________________GAUSSIAN SUMMARY:______________________________________Mean Diameter = 165.2 nm            Chi Squared = 4.236Stnd. Deviation = 64.8 nm (39.2%)            Baseline Adj. = 0.000%Coeff. of Var'n = 0.392            Mean Diff. Coeff. = 1.22E-08 cm2/s______________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US5441726 *Apr 28, 1993Aug 15, 1995Sunsmart, Inc.Topical ultra-violet radiation protectants
US5468471 *Aug 19, 1994Nov 21, 1995Estee Lauder, Inc.Titanium dioxide dispersions, cosmetic compositions and methods for using same
US5573753 *Sep 30, 1992Nov 12, 1996Tioxide Specialties LimitedMethod of preparing sunscreens
EP0535971A1 *Oct 1, 1992Apr 7, 1993Tioxide Specialties LimitedOil dispersions of zinc oxide
EP0535972A1 *Oct 1, 1992Apr 7, 1993Tioxide Specialties LimitedMethod of preparing sunscreens
EP0559319A2 *Jan 26, 1993Sep 8, 1993Tioxide Specialties LimitedOil-in-water emulsions
GB2206339A * Title not available
GB2226018A * Title not available
WO1994018940A1 *Feb 25, 1994Sep 1, 1994Estee Lauder, Inc.Titanium dioxide dispersions, cosmetic compositions and methods for using the same
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US6410614 *Mar 3, 2000Jun 25, 2002Basf CorpotationIncorporating titanium dioxide in polymeric materials
US7390922Mar 22, 2004Jun 24, 2008Kiel Laboratories, Inc.Phenolic acid salts of gabapentin in liquid and/or semi-solid dosage forms and methods of use
US7456312Mar 22, 2004Nov 25, 2008Kiel Laborities, Inc.Phenolic acid salts of gabapentin in solid dosage forms and methods of use
US7550628Mar 22, 2004Jun 23, 2009Kiel Laboratories, Inc.Process for preparing phenolic acid salts of gabapentin
US7648678Dec 8, 2003Jan 19, 2010Dako Denmark A/SMethod and system for pretreatment of tissue slides
US7687650Mar 30, 2010Jr Chem, LlcChemical compositions and methods of making them
US7758809Jul 20, 2010Dako Cytomation Denmark A/SMethod and system for pretreatment of tissue slides
US7786168Jun 13, 2008Aug 31, 2010Kiel Laboratories, Inc.Phenolic acid salts of gabapentin in solid dosage forms and methods of use
US7867522Dec 29, 2006Jan 11, 2011Jr Chem, LlcMethod of wound/burn healing using copper-zinc compositions
US7897800Mar 1, 2011Jr Chem, LlcChemical compositions and methods of making them
US7927614Jun 14, 2006Apr 19, 2011Jr Chem, LlcAnti-aging treatment using copper and zinc compositions
US7937228May 3, 2011Dako Denmark A/SInformation notification sample processing system and methods of biological slide processing
US7960178Dec 19, 2003Jun 14, 2011Dako Denmark A/SEnhanced scheduling sample processing system and methods of biological slide processing
US8148563Feb 19, 2010Apr 3, 2012Jr Chem, LlcChemical compositions and methods of making them
US8216512Dec 19, 2003Jul 10, 2012Dako Denmark A/SApparatus for automated processing biological samples
US8257968Dec 19, 2003Sep 4, 2012Dako Denmark A/SMethod and apparatus for automatic staining of tissue samples
US8273791Dec 10, 2008Sep 25, 2012Jr Chem, LlcCompositions, kits and regimens for the treatment of skin, especially décolletage
US8298815Dec 22, 2003Oct 30, 2012Dako Denmark A/SSystems and methods of sample processing and temperature control
US8386195Mar 28, 2011Feb 26, 2013Dako Denmark A/SInformation notification sample processing system and methods of biological slide processing
US8394635Mar 12, 2013Dako Denmark A/SEnhanced scheduling sample processing system and methods of biological slide processing
US8505730Aug 23, 2012Aug 13, 2013Jr Chem, LlcCompositions, kits and regimens for the treatment of skin, especially décolletage
US8529836Jun 11, 2012Sep 10, 2013Dako Denmark A/SApparatus for automated processing biological samples
US8663978Aug 6, 2012Mar 4, 2014Dako Denmark A/SMethod and apparatus for automatic staining of tissue samples
US8673642Feb 4, 2013Mar 18, 2014Dako Denmark A/SEnhanced scheduling sample processing system and methods of biological slide processing
US8784735Aug 12, 2013Jul 22, 2014Dako Denmark A/SApparatus for automated processing biological samples
US8788217Jan 23, 2013Jul 22, 2014Dako Denmark A/SInformation notification sample processing system and methods of biological slide processing
US8906961Jul 15, 2013Dec 9, 2014Segetis, Inc.Glycerol levulinate ketals and their use in the manufacture of polyurethanes, and polyurethanes formed therefrom
US8952057Jun 16, 2011Feb 10, 2015Jr Chem, LlcCompositions for anorectal use and methods for treating anorectal disorders
US8962597Mar 31, 2014Feb 24, 2015Segetis, Inc.Alkyl ketal esters as dispersants and slip agents for particulate solids, methods of manufacture, and uses thereof
US8969086Feb 18, 2014Mar 3, 2015Dako Denmark A/SEnhanced scheduling sample processing system and methods of biological slide processing
US9156809Nov 27, 2013Oct 13, 2015Segetis, Inc.Carboxy ester ketals, methods of manufacture, and uses thereof
US9229016Jun 17, 2014Jan 5, 2016Dako Denmark A/SInformation notification sample processing system and methods of biological slide processing
US20040192616 *Mar 22, 2004Sep 30, 2004Kiel Jeffrey S.Phenolic acid salts of gabapentin in solid dosage forms and methods of use
US20040192617 *Mar 22, 2004Sep 30, 2004Kiel Jeffrey S.Process for preparing phenolic acid salts of gabapentin
US20040192618 *Mar 22, 2004Sep 30, 2004Kiel Jeffrey S.Phenolic acid salts of gabapentin in liquid and/or semi-solid dosage forms and methods of use
US20040234593 *Feb 26, 2003Nov 25, 2004Kiel Jeffrey SDiphenhydramine tannate compositions and methods of use
US20050069584 *Feb 26, 2003Mar 31, 2005Kiel Jeffrey SDiphenhydramine tannate solid dose compositions and methods of use
US20060008536 *Jul 8, 2004Jan 12, 2006Jdc PharmaceuticalPharmaceutical compositions and methods of use
US20060085140 *Dec 19, 2003Apr 20, 2006Gordon FeingoldInformation notification sample processing system and methods of biological slide processing
US20060088928 *Dec 19, 2003Apr 27, 2006Dakocytomation Denmark A/SMethod and apparatus for automatic staining of tissue samples
US20060204456 *Nov 21, 2003Sep 14, 2006Takashi AsakuraTitanium oxide particles having useful properties and method for production thereof
US20080242728 *Jun 13, 2008Oct 2, 2008Kiel Jeffrey SPhenolic acid salts of gabapentin in solid dosage forms and methods of use
US20090185752 *Jan 22, 2009Jul 23, 2009Digital Business Processes, Inc.Method and apparatus for cropping images
US20110224329 *Jan 6, 2009Sep 15, 2011Dow Global Technologies LlcMetal stabilizers for epoxy resins and dispersion process
WO2011143255A2 *May 10, 2011Nov 17, 2011Segetis, Inc.Alkyl ketal esters as dispersants and slip agents for particulate solids, methods of manufacture, and uses thereof
WO2011143255A3 *May 10, 2011Apr 19, 2012Segetis, Inc.Alkyl ketal esters as dispersants and slip agents for particulate solids, methods of manufacture, and uses thereof
WO2013117642A1 *Feb 7, 2013Aug 15, 2013Ley & Co. Farbenwerke Wunsiedel KGAcid-resistant coated pigments
WO2015091133A1 *Dec 10, 2014Jun 25, 2015Societe Industrielle Liegeoise Des Oxydes SaVulcanization additive composition
Classifications
U.S. Classification424/59, 424/614, 424/641, 424/401, 424/67, 424/642, 424/70.9
International ClassificationA61Q1/12, C09C1/36, A61Q1/08, C09C1/24, A61K8/19, A61Q17/04, A61K8/27, C09D17/00, A61Q1/06, C09C3/04, A61Q1/10, A61K8/29, C09C1/04, A61K8/04
Cooperative ClassificationC09C1/24, A61Q1/06, C01P2004/62, A61K8/19, C09C3/041, A61K8/044, A61Q1/08, C09C1/043, B82Y30/00, C01P2004/64, A61K8/29, C01P2004/61, C09D17/007, C01P2004/51, A61Q1/12, C01P2006/80, A61K8/27, A61Q17/04, C09C1/3623, C01P2006/19, C01P2006/60, C01P2006/12, A61Q1/10, C01P2002/84
European ClassificationB82Y30/00, A61K8/27, A61K8/29, A61Q1/06, A61Q17/04, A61K8/19, A61Q1/12, C09D17/00J6, C09C1/24, A61Q1/08, C09C1/36D4B, C09C3/04B, A61Q1/10, C09C1/04B, A61K8/04C
Legal Events
DateCodeEventDescription
May 6, 1998ASAssignment
Owner name: ELLIS, DAVID GRAHAM, AUSTRALIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ELLIS, DAVID GRAHAM;BOS, MICHAEL ARY;REEL/FRAME:009702/0381
Effective date: 19980505
Owner name: M & J BOS CONSULTANTS PTY LTD., AUSTRALIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ELLIS, DAVID GRAHAM;BOS, MICHAEL ARY;REEL/FRAME:009702/0381
Effective date: 19980505
May 1, 2001CCCertificate of correction
Sep 17, 2003FPAYFee payment
Year of fee payment: 4
Nov 27, 2007FPAYFee payment
Year of fee payment: 8
Dec 21, 2011FPAYFee payment
Year of fee payment: 12